Substantive orthooxyazo dyestuffs and a process of making same.



5 Swiss Republic, and residents of Basel,

me This application is a divisional one of our aut a =1 unuuran' r nrrzscue, Hnru'arcu scnonrm, or wer WJLZERLAND. Y eunsra vrryn ou'ruoourazo nrns'rurrs a raocnss or m G SMKE.

C ASSIGNUES T0 SOCIETY OF CHEMICAL INDUSTRY Illly aay pay Specification 0t hettersratent. 1 I Patented May t, rarer life mrevvllna. urlalnal application filed uctoher c, new, Serial No. Mallet. Divided and this application filed January 24, 11917. heral Ito. iaaaaa p Toallwhomitmaycoacem: I pp Be it known that we, Eueru Anneuwn ar, HERMAN Fmrzsoiun, and Hemmer: Sono- BEL, all three chemists and citizens of the Switzerland, have invented new Substantive Urthooxyazo Dyestuds and a Process of Making Same, of whichvthe following is a full; clear, and exact specification;

-- application for Letters Patent Ser. Ne

5 1L403, filed October 6, 1915.

-Urthoaminophenoland its derivatives have teen employed hitherto exclusively for it the manufacture of orthooxyazodyestufis' dyein mord'anted wool, and never for the menu acture of substantive dyestufls-d eing ,unmordanted cotton. We have now ound 1 that the azodyestufl's containing the diazodeac rivative of orthoarninophenol or of one of its derivatives and a 2 z 5 'i-aminonapththolsultonic or 2:5:lzT-aminonaphtho disullonic compound coupled together by vthe diazoderivative ot a primary monoamin havin at relatively to the amino oup a non-suheti- I tuted position para, as or instance alpha naphthylamim acid of tlleve, para-cresidin, acetylmetatoluylenediamin and aminophenyloxarnic acid, have the properties of sully ac stantive azodyestufi's, that is to dye cotton and other fihers without inordant.

Besides the 2:5:7-aminoriaphtholmono .sull'onic or 2:521:7-aminonaphtholdisulionic acid one of the following derivatives of at 2:5zi'eaminonapththolmonosulfonic acid can he employedzso u y /N =c-om w am. \/k/ H l v e or one of the corresponding derivatives of the 2:5:1:7-aminonaphtholdisulfonic acid.

The new orthooxyazodyestulfs derived" in the aforesaid manner from these 2:5:7- aminonaphtholsulfonic or 2: 5: 1: 7-amino naphtholdisulfonic compounds constitute intense colored powders, yielding with concentrated sulfuric acid deep colored solutions and dissolving in water to solutions changing intensively their coloration on addition of sodium carbonate or of soda lye and dyeing cotton, wool, silk, mixed goods, straw, wood and paper according to the methods used for the known substantive dyestuffs.

The invention is illustrated by the followingEexamples:

xample 1: To the diazoderivative of 18.9 kg. orthoaminophenolsulfonic acid is added the solution of 14.3 kg. alphanaphthylaniin in water and 12 kg. hydrochloric acid. The formation of the monoazodyestuff is achieved by stirring at 3040 C. for a long time. For the purpose of a further diazotizing of the monoazodyestufl, it is transformed, after addition of common salt, into the sodium salt by means of soda lye. To this sodium salt are added at first 7.5 kg. sodium nitrite and afterward quickly 40 kg. hydrochloric acid. After a stirring for 1 hour, the diazo-compound is filtered and poured into a solution of 36 kg. metaaminoenzoyl-2 :5 :7 -aminonaphtholsulfonic acid and of 40 kg. sodium carbonate in water.

The dyestufi' isolated in the usual way dyes a and of 40 cotton reddish-blue tints and dissolves in water to a bluish-violet solution turning to blue on addition of NaOH.

Example 2: The diazoderivative of 19.9

- kg. picramic acid is combined with a solution of 22.3 kg. acid of Cleve and 30 kg. crystallized sodium acetate; the combination is achieved after 24 hours. By transformation into sodium salt, addition of 7.5 kg. sodium nitrite and acidulating with hydrochloric acid the further diazotizin is effected. After a stirring for a long time, the diazocompound is freed from water by suction, transformed again into a paste and poured into a solution'of 25.2 kg.

/ SOIH kg. sodium carbonate in water. The dyestuif salted out by common salt yields on cotton dull blue tints and dissolves nol are diazotized in the usual manner and the thus obtained diazocompound is added to a solution of 22.3 kg. acid of Cleve and 30 kg. crystallized sodium acetate in water. After stirring for a long time, the combination is achieved by warming to 3040 C. The monoazodyestuff is after acidulating directly further diazotized with 7.2 kg. sodium nitrite, the resulting diazoazocompound after 2 hours dried by suction, again stirred with water and poured into a solution of 22.3 kg. acid of Cleve and 20 kg. crystallized sodium acetate in water. Before the further diazotation, the thus obtained diazodyestufi' is advantageously at first precipitated and separated by filtration and then dissolved again and diazotized again by addition of 40 kg. hydrochloric acid and 7 kg. sodium nitrite. After a stirring of 2 hours the diazoazocompound is poured into a solution of 24 k 2: 5:7 -aminonaphtholsulfonic acid and 40. g. sodium carbonate in water. The dyestufi isolated in the usual manner yields on cotton green-blue tints and dissolves in water to a blue solution.

Instead of the aminophenol derivatives indicated in the examples, can be employed the corresponding diazoacidylphenol derivatives able to combine more easily, the resulting dyestufis being saponified after their preparation.

The new dyestuffs are not only suitable for dyeing cotton, wool, silk, leather, straw, wood, paper, mixed oods etc. like the known substantive dyestu s, but also for the production of lakes and as parent materials for the production of valuable new derivatives.

What we claim is:

1. The described process for the manufacture of new substantive orthooxyazodyestufis consistin in combining an aromatic orthooxydiazo ody with a primary monoamin having relatively to the amino group a nonsubstituted position para, diazotizing the resulting intermediate product and combining the resulting diazoazocompound with a 2: 5 7 -aminonaphthosulf0nic compound.

2. The described process for the manufacture of new substantive orthooxyazodyestufis consistin in combining an aromatic orthooxydiazo dy with a primary monoamin having relatively to the amino up a non substituted position para, diazotizing the resulting intermediate product and combining the resulting diazoazocom ound with a 2:5:1:7 aminonaphthol onic compound.

3. The described process for the manufacture of new substantive orthooxyazodyestuffs, consisting in combining an aromatic with a primary mononaeaoar a, having relatively tothe ao' oup a non substituted position para, diazotizing the thus obtained intermediate product, com- ,aminonaphtholsulfonic comtpound.

t. The described process or the manufacture of new substantive orthooxyazodye- I stufis consisting in combining an aromatic orthooxydiazobody with a primary monoamin havin relatively'to the amino group a non substltuted position para, diazotizing the thus obtained intermediate product, comjbining the resulting diazoazocompound again with a primary monoamin having relatively to the amino group a non substituted position para, diazotizing the resulting intermediate product and combining the thus obtained diazobody with naphtholdisulfonic compound.

5. As new products, the herein described new substantive orthooxyazodyestuds containing an aromatic orthooxydiazobody and a 2: 5 'l-aminonaphtholsulionic compound coupled together by the diazoderivative of a primary monoamin having relativel to the amino group a non substituted position para and constituting intense colored powders, yielding with concentrated $2!" 1:" a id a 2:5:1:7-amino-' deep colored solutions, dissolving in we to solutions chang intensively their coloration on addition of sodium carbonate or of soda lye and dyeing cotton, wool, silk, min goods, straw, wood andpaper, .ir g to the methods used for the known substantive dyestufis. x

6. As new products, the herein described new substantive orthooxyazodyestuds containing an aromatic orthooxydiazobody and a 2 5:1:7- aminonaphtholdisulfonic compound coupled together by the diazoderivative of a primary monoa having relatively to the amino group a non substitu position para and constituting intense colorcd powders, yielding with concentrated sulfuric acid deep colored solutions, dissolving in water to solutions changing intensively their coloration on addition of sodium carbonate or of soda lye and dyeing cotton, wool, silk, ed goods, straw, wood and paper, according to the methods used for the known substantive dyestnd's,

In witness whereof we have hereunto signed our names this 23rd day of Deber 1916, in the presence of two subscribing witnesses.

' EUGEN ERRT, R FRHVLSG. lhIRlCH SCHUBEL,

With to G U, Spa time ND R 1! Mt 

